Smolyaninov Ivan V, Poddel'sky Andrey I, Smolyaninova Susanna A, Arsenyev Maxim V, Fukin Georgy K, Berberova Nadezhda T
Toxicology Research Group, Federal State Budgetary Institution of Science "Federal Research Centre The Southern Scientific Centre of the Russian Academy of The Sciences", Tatischeva str. 16, 414056 Astrakhan, Russia.
Department of Chemistry, Astrakhan State Technical University, 16 Tatisheva str., Astrakhan 414056, Russia.
Molecules. 2020 Apr 12;25(8):1770. doi: 10.3390/molecules25081770.
New polyfunctional sterically hindered 3,5-di--butylcatechols with an additional phenolic group in the sixth position connected by a bridging sulfur atom-(6-(CH-S-tBuPhenol)-3,5-DBCat)H (), (6-(S-tBuPhenol)-3,5-DBCat)H (), and (6-(S-Phenol)-3,5-DBCat)H () (3,5-DBCat is dianion 3,5-di--butylcatecolate)-were synthesized and characterized in detail. The exchange reaction between catechols and with triphenylantimony(V) dibromide in the presence of triethylamine leads to the corresponding triphenylantimony(V) catecholates (6-(CH-S-tBuPhenol)-3,5-DBCat)SbPh () and (6-(S-Phenol)-3,5-DBCat)SbPh (). The electrochemical properties of catechols - and catecholates and were investigated using cyclic voltammetry. The electrochemical oxidation of - at the first stage proceeds with the formation of the corresponding -benzoquinones. The second process is the oxidation of the phenolic moiety. Complexes and significantly expand their redox capabilities, owing to the fact that they can act as the electron donors due to the catecholate metallocycle capable of sequential oxidations, and as donors of the hydrogen atoms, thus forming a stable phenoxyl radical. The molecular structures of the free ligand and complex in the crystal state were determined by single-crystal X-ray analysis.
新型多官能团位阻3,5 - 二叔丁基儿茶酚，在第六位带有一个额外的酚羟基，通过桥连硫原子相连 - (6-(CH - S - tBuPhenol)-3,5 - DBCat)H (), (6-(S - tBuPhenol)-3,5 - DBCat)H (), 和(6-(S - Phenol)-3,5 - DBCat)H () (3,5 - DBCat是二价阴离子3,5 - 二叔丁基儿茶酚酸根) - 已被合成并进行了详细表征。在三乙胺存在下，儿茶酚 和 与三苯基锑(V)二溴化物之间的交换反应生成相应的三苯基锑(V)儿茶酚酸盐(6-(CH - S - tBuPhenol)-3,5 - DBCat)SbPh () 和(6-(S - Phenol)-3,5 - DBCat)SbPh ()。使用循环伏安法研究了儿茶酚 - 以及儿茶酚酸盐 和 的电化学性质。儿茶酚 - 在第一阶段的电化学氧化过程中生成相应的 - 苯醌。第二个过程是酚羟基部分的氧化。配合物 和 显著扩展了它们的氧化还原能力，这是因为它们能够作为电子供体，由于儿茶酚酸根金属环能够进行连续氧化，并且还能作为氢原子供体，从而形成稳定的苯氧自由基。通过单晶X射线分析确定了晶体状态下游离配体 和配合物 的分子结构。
